[Ni(py)3(SHSH)]·1.5(py)的合成、晶体结构及电化学性质研究

以DMF和吡啶为溶剂合成了镍的水杨醛缩水杨酰肼Schiff碱(SHSH)的配合物[Ni(py)₃(SHSH)]·1.5(py)(其中py代表吡啶)，成功培养出了单晶。通过UV、IR、元素分析和X射线衍射等进行了表征。中心镍离子与Schiff碱提供的2个氧原子和1个氮原子以及3个溶剂吡啶的氮原子参与了配位，形成了六配位的变形八面体构型，存在分子内氢键和分子间氢键。晶体属单斜晶系，空间群：P2₁/n。采用循环伏安法研究了其在吡啶和DMF溶液中的电化学性质。     

电荷转移盐(C_3H_5N_2H)_3[PMo_(12)O_(40)]的合成与热分解及光致变色反应动力学

用磷钼酸与咪唑合成了一种新的杂多酸-有机电荷转移盐(C3H5N2H)3[PMo12O40]。通过元素分析、红外光谱、固体漫反射光谱、电子自旋共振及热分析等测试技术对其进行了表征,用单扫描法(Achar法和Coats-Redfern法)对合成化合物的TG分析结果进行了非等温热分解动力学研究。推断结果表明,合成化合物的第1步热分解为球对称的三维扩散机理(n=2),其动力学方程为dα/dt=1.58×108[1-(1-α)1/3]-1(1-α)2/3exp(-40931.0/T),求得分解反应的表观活化能E=340.30kJ/mol,指前因子A=1.05×108s-1。标题化合物对紫外光具有光致变色性质,用固体漫反射光谱研究了其光致变色反应动力学。结果显示,其光致变色反应表现为一级或准一级动力学,速率常数k=9.80×10-5s-1。     

Cr4+∶YAG晶体的激发态吸收研究

对Cr4 + ∶YAG晶体作为 10 6 4nm激光的可饱和吸收体进行了研究。利用速率方程 ,描述了强激光下晶体的激发态吸收 (ESA)的动力学过程。用实验验证了所导出的光强与透过率的理论曲线 ,并因此论证了可以利用晶体的激发态吸收进行激光调Q ,并对其进行优化。     

Synthesis, computational modeling, and properties of benzo-appended BODIPYs

A series of new functionalized mono- and dibenzo-appended BODIPY dyes were synthesized from a common tetrahydroisoindole precursor following two different synthetic routes. Route?A involved the assembly of the BODIPY core prior to aromatization, while in Route?B the aromatization step was performed first. In general, Route?A gave higher yields of the target dibenzo-BODIPYs, due to the ease of aromatization of the BODIPYs compared with the corresponding dipyrromethenes, probably due to their higher stability under the oxidative conditions (2,3-dichloro-5,6-dicyano-1,4-benzoquinone in refluxing toluene). However, due to the slow oxidation of highly electron-deficient BODIPY 3?c bearing a meso-C(6)F(5) group, dibenzo-BODIPY 4?c was obtained, in 35?% overall from dipyrromethane, only by Route?B. Computational calculations performed at the 6-31G(d,p) level are in agreement with the experimental results, showing similar relative energies for all reaction intermediates in both routes. In addition, BODIPY 3?c had the highest molecular electrostatic potential (MEPN), confirming its high electron deficiency and consequent resistance toward oxidation. X-ray analyses of eight BODIPYs and several intermediates show that benzannulation further enhances the planarity of these systems. The π-extended BODIPYs show strong red-shifted absorptions and emissions, about 50-60?nm per benzoannulated ring, at 589-658 and 596-680?nm, respectively. In particular, db-BODIPY 4?c bearing a meso-C(6)F(5) group showed the longest λ(max) of absorption and emission, along with the lowest fluorescence quantum yield (0.31 in CH(2)Cl(2)); on the other hand monobenzo-BODIPY 8 showed the highest quantum yield (0.99) of this series. Cellular investigations using human carcinoma HEp2 cells revealed high plasma membrane permeability for all dibenzo-BODIPYs, low dark- and photo-cytotoxicities and intracellular localization in the cell endoplasmic reticulum, in addition to other organelles. Our studies indicate that benzo-appended BODIPYs, in particular the highly stable meso-substituted BODIPYs, are promising fluorophores for bioimaging applications.     

Programmable multiple true-time-delay elements based on a Fourier-domain optical processor

A new technique to realize an array of multiple true-time-delay elements, which can be independently and continuously tuned, is reported. It is based on a WDM parallel signal processing approach in conjunction with a diffraction-based Fourier-domain optical signal processor. Programmable linear optical phase transfer functions are realized to obtain different electrical true-time delays. The technique can scale to a large number of wideband true-time-delay lines, with continuously tunable programmable delay. Results demonstrate multiple true-time-delay elements with independent tuning control and verify the concept by tuning the free spectral range of a microwave photonic notch filter. To our best knowledge, this is the first demonstration of multiple independently controllable true-time-delay lines for microwave photonic systems.     

Quantum chemistry studies of adenosine 2503 methylation by S‐adenosylmethionine‐dependent enzymes

Ribosome methylation is important for life processes and is mainly catalyzed by radical S‐Adenosylmethionine (SAM) enzymes. Two SAM molecules serve as the cofactor by providing the 5 ′‐deoxyadenosyl radical for substrate activation and the methyl. Recently, Booker and coworkers (Science 2011, 332, 604) proposed an alternative mechanism for a pair of radical SAM enzymes, RlmN and Cfr, which respectively methylate the C2 and C8 of adenosine 2503. Their deuterium labeling experiments reveal that methyl group does not transfer directly from SAM to adenosine, instead it passes to Cys³⁵⁵ first, then onto adenosine. In this article, this new reaction mechanism is studied using density functional theory with B3LYP hybrid functional. The reaction system is simulated using small model compounds in the gas phase, and the protein environment is approximated using polarizable continuum model. The structures of the transition states and the intermediates are identified, and their free energies are calculated. The activation barriers indicate that the proposed reaction mechanism is plausible. The formation of a disulfide bond is found to be the rate‐limiting step. © 2012 Wiley Periodicals, Inc.     

Nanogel Multienzyme Mimics Synthesized by Biocatalytic ATRP and Metal Coordination for Bioresponsive Fluorescence Imaging

The design of enzyme mimics from stable and nonprotein systems is especially attractive for applications in highly specific cancer diagnosis and treatment, and it has become an emerging field in recent years. Herein, metal crosslinked polymeric nanogels (MPGs) were prepared using Fe^II ion coordinated biocompatible acryloyl‐lysine polymer brushes obtained from an enzyme‐catalyzed atomic transfer radical polymerization (ATRPase) method. The monoatomic and highly dispersed Fe ions in the MPGs serve as efficient crosslinkers of the gel network, and also as active centers of multienzyme mimics of superoxide dismutase (SOD) and peroxidase (POD). The catalytic activities were compared to those of conventional Fe‐based nanozymes. Studies on both cells and animals verify that efficient reactive oxygen species (ROS) responsive biofluorescence imaging can be successfully realized using the MPGs.     

Large‐Scale Production of Homogeneous Helical Amylose/SWNTs Complexes with Good Biocompatibility

The key to developing novel applications of SWNTs in biotechnology and biomedicine is to improve their biocompatibility and solubility in water and to assemble them into useful architectures. We describe how amylose can help to solubilize SWNTs and wrap around SWNTs into helical superstructures with periodic pitch. FT‐IR, Raman spectroscopy, ¹H NMR and HR‐TEM are used to confirm the generation of amylose/SWNTs complexes (A/S‐C). It is demonstrated that most of the A/S‐C have similar diameters (ca. 20–30 nm) and a helical morphology with a pitch of ca. 14 nm. A test of Hela cell viability revealed that the A/S‐C had much better biocompatibility than SWNTs.

     

含Dawson结构杂多钨磷(砷)酸电荷转移配合物的合成、结构与性质

近年来,有机多金属氧酸盐电荷转移配合物由于有特殊的光、电、磁性质在催化、功能材料及药物化学等领域受到研究者的广泛关注［１］。自从１９８８年法国的Ｌ．Ｏｕａｈａｂ［２］首次报道（ＴＴＦ）６ＰＷ１２Ｏ４０（Ｅｔ４Ｎ）２的合成以来,已见报道的多金属氧酸盐仅限于ＡｎｄｅｒｓｏｎＥｖａｎｓｅ、ｌｉｎｄｑｕｉｓｔ和Ｋｅｇｇｉｎ结构的多阴离子,对它们功能性质的系统研究也未见文献报道。为了研究阴离子的大小和形状对标题化合物功能性质的影响,作者在以前工作的基础上［３,４］,首次以Ｄａｗｓｏｎ结构杂多钨磷（砷）…